(cis)-1-benzoyl-(trans)-2-nitro-3-phenylcyclopropane | 6277-65-2

• 分子结构分类: 有机化合物 - 有机氧化合物
• 英文名称: (cis)-1-benzoyl-(trans)-2-nitro-3-phenylcyclopropane
• 英文别名: [(1S,2S,3S)-2-nitro-3-phenylcyclopropyl]-phenylmethanone
• CAS: 6277-65-2
• 化学式: C₁₆H₁₃NO₃
• 分子量: 267.284
• InChiKey: ZFAHRSYYEJMLHM-ILXRZTDVSA-N

物化性质

• 熔点：
  98 °C(Solv: ethanol (64-17-5))
• 沸点：
  441.6±45.0 °C(Predicted)
• 密度：
  1.28±0.1 g/cm3(Predicted)

计算性质

• 辛醇/水分配系数(LogP)：
  2.9
• 重原子数：
  20
• 可旋转键数：
  3
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.19
• 拓扑面积：
  62.9
• 氢给体数：
  0
• 氢受体数：
  3

反应信息

• 作为产物：
  描述：

  (2S,3S)-2-Bromo-4-nitro-1,3-diphenyl-butan-1-one 在 三乙胺 作用下， 以 氘代二甲亚砜 、 重水 为溶剂， 生成 (cis)-1-benzoyl-(trans)-2-nitro-3-phenylcyclopropane
  参考文献：
  名称：

  D/H Exchange in Nitro Diastereomers

  摘要：

  The two diastereomers of 4-nitro-1,3-diphenylpentan-1-one behave differently in deuterium for hydrogen exchange in DMSO-d(6)/D2O solutions using various bases as catalyst. Reaction of the erythro diastereomer gives largely the same diastereomer upon D/H exchange (retention), i.e., exchange exceeds epimerization. Pyridine and acetonitrile as solvents lead to faster epimerization than exchange. In the three diastereomer(DMSO-d(6) solution), epimerization exceeds exchange, and the anion to some extent regains the same hydrogen originally removed by the base on the opposite face. 2-Bromo-4-nitro-1,3-diphenylbutan-1-one undergoes ring closure to the cyclopropane faster than exchange (within seconds). The cyclopropane shows faster exchange than equilibration, i.e., retention of configuration, although it is the hydrogen alpha to carbonyl that is involved.

  DOI：

  10.1021/jo9717402

文献信息

• Enantioselective Synthesis of Functionalized Nitrocyclopropanes by Organocatalytic Conjugate Addition of Bromonitroalkanes to α,β-Unsaturated Enones
  作者：Jian Lv、Jiaming Zhang、Zhu Lin、Yongmei Wang

  DOI：10.1002/chem.200801651

  日期：2009.1.12

  A general enantioselective synthesis of functionalized nitrocyclopropanes by organocatalytic conjugate addition of a variety of bromonitroalkanes to α,β‐unsaturated enone systems is presented. The process, efficiently catalyzed by the salts of 9‐amino‐9‐deoxyepiquinine 1 d serves as a powerful approach to the preparation of synthetically and biologically important cyclopropanes with high levels of

  提出了通过将各种溴硝基烷烃有机共轭加成到α，β-不饱和烯酮体系中来官能化硝基环丙烷的一般对映选择性合成方法。该过程可通过9-氨基-9-脱氧表奎宁1 d的盐有效催化，是制备具有高对映异构和非对映异构选择性的合成和生物学上重要的环丙烷的有力方法。由于仅使用0.6当量的溴硝基甲烷作为试剂，通过使用手性1 d作为其动力学拆分的高效催化剂，对映体纯（S）-2 e（97％  ee在51％转化率下，选择性s = 120） 。
• Vicarious nucleophilic substitution of hydrogen in electrophilic alkenes
  作者：Mieczysłlaw Ma̧kosza、Andrzej Kwast

  DOI：10.1016/s0040-4020(01)80963-7

  日期：1991.1

  Carbanions containing leaving groups react in the presence of base with electrophilic alkenes giving products in which vinylic hydrogen is replaced with the carbanion moiety. They are formed via addition - β-elimination pathway analogous to the vicarious nucleophilic substitution in nitroarenes. In some cases, however, the cyclization - ring opening process takes place instead.

  含有离去基团的碳负离子在碱的存在下与亲电子烯烃反应，生成产物，其中乙烯基氢被碳负离子部分取代。它们是通过加成-消除途径形成的，类似于硝基芳烃中的替代性亲核取代反应。但是，在某些情况下，会发生环化-开环过程。
• D/H Exchange in Nitro Diastereomers
  作者：Charles A. Kingsbury

  DOI：10.1021/jo9717402

  日期：1998.6.1

  The two diastereomers of 4-nitro-1,3-diphenylpentan-1-one behave differently in deuterium for hydrogen exchange in DMSO-d(6)/D2O solutions using various bases as catalyst. Reaction of the erythro diastereomer gives largely the same diastereomer upon D/H exchange (retention), i.e., exchange exceeds epimerization. Pyridine and acetonitrile as solvents lead to faster epimerization than exchange. In the three diastereomer(DMSO-d(6) solution), epimerization exceeds exchange, and the anion to some extent regains the same hydrogen originally removed by the base on the opposite face. 2-Bromo-4-nitro-1,3-diphenylbutan-1-one undergoes ring closure to the cyclopropane faster than exchange (within seconds). The cyclopropane shows faster exchange than equilibration, i.e., retention of configuration, although it is the hydrogen alpha to carbonyl that is involved.